Correlated shapeshifting and configurational isomerization.

Herein we demonstrate that the rapid 'shapeshifting' constitutional isomerization of a substituted bullvalene is influenced by the E -to- Z configurational isomerization of a remote carbamate group, giving rise to correlated motion. We find that, while the E -configurational isomer of a bulky carbamate favors the β -bullvalene constitutional isomer, a noncovalent bonding interaction within the Z -carbamate tips the equilibrium toward the γ -bullvalene form. Using DFT modelling and NMR spectroscopy, this long-range interaction is identified as being between the bullvalene core and a pendant phenyl group connected to the carbamate. Coupling the constitutional changes of a bullvalene to a reciprocal configurational isomerization through a long-range interaction in this way will allow shapeshifting rearrangements to be exploited as part of collective motion in extended structures.